JPH01501316A - Production method of alginate (polyuronide) with changed physical properties - Google Patents
Production method of alginate (polyuronide) with changed physical propertiesInfo
- Publication number
- JPH01501316A JPH01501316A JP62505868A JP50586887A JPH01501316A JP H01501316 A JPH01501316 A JP H01501316A JP 62505868 A JP62505868 A JP 62505868A JP 50586887 A JP50586887 A JP 50586887A JP H01501316 A JPH01501316 A JP H01501316A
- Authority
- JP
- Japan
- Prior art keywords
- alginate
- physical properties
- polyuronide
- production method
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 235000010443 alginic acid Nutrition 0.000 title claims description 22
- 229920000615 alginic acid Polymers 0.000 title claims description 22
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 title claims description 21
- 229940072056 alginate Drugs 0.000 title claims description 20
- 230000000704 physical effect Effects 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims 2
- 230000004048 modification Effects 0.000 claims 2
- 229920002567 Chondroitin Polymers 0.000 claims 1
- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 claims 1
- DLGJWSVWTWEWBJ-HGGSSLSASA-N chondroitin Chemical compound CC(O)=N[C@@H]1[C@H](O)O[C@H](CO)[C@H](O)[C@@H]1OC1[C@H](O)[C@H](O)C=C(C(O)=O)O1 DLGJWSVWTWEWBJ-HGGSSLSASA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000011010 flushing procedure Methods 0.000 claims 1
- 229920000669 heparin Polymers 0.000 claims 1
- 229960002897 heparin Drugs 0.000 claims 1
- 238000002715 modification method Methods 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- 238000006345 epimerization reaction Methods 0.000 description 8
- 239000000499 gel Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 3
- 239000000010 aprotic solvent Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- AEMOLEFTQBMNLQ-SYJWYVCOSA-N (2s,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-SYJWYVCOSA-N 0.000 description 2
- AEMOLEFTQBMNLQ-BZINKQHNSA-N D-Guluronic Acid Chemical compound OC1O[C@H](C(O)=O)[C@H](O)[C@@H](O)[C@H]1O AEMOLEFTQBMNLQ-BZINKQHNSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 230000002255 enzymatic effect Effects 0.000 description 2
- 230000009144 enzymatic modification Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000000338 in vitro Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 1
- AEMOLEFTQBMNLQ-AZLKCVHYSA-N (2r,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-AZLKCVHYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 241000512259 Ascophyllum nodosum Species 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 241000024244 Chelis Species 0.000 description 1
- AEMOLEFTQBMNLQ-VANFPWTGSA-N D-mannopyranuronic acid Chemical compound OC1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-VANFPWTGSA-N 0.000 description 1
- 229920002683 Glycosaminoglycan Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- IAJILQKETJEXLJ-SQOUGZDYSA-N L-guluronic acid Chemical compound O=C[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O IAJILQKETJEXLJ-SQOUGZDYSA-N 0.000 description 1
- 241000296380 Laminaria hyperborea Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920002201 Oxidized cellulose Polymers 0.000 description 1
- 241000199919 Phaeophyceae Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- AEMOLEFTQBMNLQ-WAXACMCWSA-N alpha-D-glucuronic acid Chemical compound O[C@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-WAXACMCWSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000648 calcium alginate Substances 0.000 description 1
- 235000010410 calcium alginate Nutrition 0.000 description 1
- 229960002681 calcium alginate Drugs 0.000 description 1
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 229920002674 hyaluronan Polymers 0.000 description 1
- 229960003160 hyaluronic acid Drugs 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 108010084926 mannuronan c-5-epimerase Proteins 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229940107304 oxidized cellulose Drugs 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0084—Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0063—Glycosaminoglycans or mucopolysaccharides, e.g. keratan sulfate; Derivatives thereof, e.g. fucoidan
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
(57)【要約】本公報は電子出願前の出願データであるため要約のデータは記録されません。 (57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】 物理的性質を変化させたアルギネート 本発明は機能性、特に無機および有機多価イオンによるゲル形成能力について変 化を得るためにアルギネートおよび他のウロン酸物質を修飾する方法に関する。[Detailed description of the invention] Alginate with changed physical properties The present invention has been modified in terms of functionality, particularly the ability to form gels with inorganic and organic multivalent ions. The present invention relates to a method for modifying alginate and other uronic acid materials to obtain oxidation.
アルギネートは褐藻海藻類から製造され、これらの多価電解性が例えばゲル化、 増粘および水−およびイオン−結合に対する基礎を形成するいくつかの適用に利 用される。Alginates are produced from brown seaweeds, and their polyelectrolytic properties result in e.g. gelation, Useful in some applications forming the basis for thickening and water- and ionic-bonding. used.
化学的には、アルギネートはβ−Ｄ−マンヌロン酸（Ｍ）およびそのＣ−５エピ マー、α−Ｌ−グルロン酸（Ｇ）から形成される１群の直鎖、二元共重合体を構 成する。ＭおよびＧユニットは３種のタイプの配列で見出される。Ｇ−ブロック と呼ばれるＧの豊富な配列、Ｍ−ブロックと呼ばれるＭの豊富な配列、およびＭ Ｇ−ブロックに見出される交互の配列、ＭＧＭＧとして記号化されるものである 。これらのモノマー ユニットおよびこれらの配列配分のフラクション含量は海 草起源により変化する。イオン結合およびゲル形成性はモノマーフラクションに 依るが、特に鎖に沿うＧ−ユニットの配分による。Ｇ−ブロックの高含量は技術 上ｆｆ要なゲル形成性に導く。Chemically, alginate is composed of β-D-mannuronic acid (M) and its C-5 epi A group of linear, binary copolymers formed from α-L-guluronic acid (G) to be accomplished. M and G units are found in three types of arrangements. G-block G-rich sequences called M-blocks, M-rich sequences called M-blocks, and M-rich sequences called M-blocks. The alternating sequence found in the G-block, symbolized as MGMG . The fractional content of these monomer units and their sequence distribution is Varies depending on grass origin. Ionic binding and gel-forming properties are determined by the monomer fraction. It depends, especially on the distribution of G-units along the chain. High content of G-block is technology Leads to the necessary gel-forming properties.
本発明の目的はこれらの物理性を変えるために、オリゴマー又はポリマーのＭ− ユニットをＧ−ユニットに転換することである。もとの完全なポリマーのこのタ イプのエンド−エピマー化はマンヌロナンＣ−５エピメラーゼ、アルギネートの 生体内住合成に関与する酵素（出願番号８４５０５９参照）によりアルギネート を処理することにより行なうことができる。The purpose of the present invention is to modify the M- It is to convert a unit into a G-unit. This type of original complete polymer The endo-epimerization of alginate is carried out by mannuronan C-5 epimerase. alginate by enzymes involved in biosynthesis (see application number 845059). This can be done by processing.
本発明によれば、いくつかのポリサッカライド生産微生物からの酵素方法として 周知のこのようなエピマー化は酵素がなくても行なうことができる。この種の方 法は、カルボアニオン（Ｃ−５における電荷）を生成する；］−５のアルカリ触 媒抽出は水の存在でポリマー鎖の加水分ネート）は非極性溶媒に不溶性であり、 従って非プロトン性溶媒中の反応は実施が困難である。According to the present invention, as an enzymatic method from some polysaccharide producing microorganisms Such epimerization, which is well known, can be carried out without enzymes. This kind of person The method produces a carbanion (charge at C-5); Solvent extraction is the presence of water in which the polymer chains (hydronate) are insoluble in non-polar solvents; Therefore, reactions in aprotic solvents are difficult to carry out.
本発明は超臨界條件下で二酸化炭素により固体状態でアルギネートを処理するこ とにより上記問題を排除する完全に新しい原理に基づく。この條件は密度は液状 であるが、拡散速度はガス状態における場合と同じである。The present invention involves treating alginate in the solid state with carbon dioxide under supercritical conditions. and is based on a completely new principle that eliminates the above problems. This condition means that the density is liquid However, the diffusion rate is the same as in the gaseous state.
その場合ＣＯ２は非プロトン性溶媒として、および触媒としての双方でＨ−５の アルカリ除去に作用しＣ−５カルボアニオンを形成することができる。高圧はシ アキシアルに（ｄｉａｘｉａｌｌｙ ）結合したＧ−ユニットが一層緊密な鎖構 造、従ってジイクアトリアルに（ｄｔｅｑｕａｔｏｒｉａｌｌｙ）結合したＭ− ユニットと対比して低級部分モル容積を与えるように、効果的にエピマー化に寄 与する。ざらに非プロトン性溶媒中で７ノマー効果はアルギネートのα−一層有 利にする。In that case CO2 is used both as an aprotic solvent and as a catalyst for H-5. It can act on alkali removal and form a C-5 carbanion. High pressure is The axially bonded G-units form a tighter chain structure. structure, thus diquatorially coupled M- effectively contribute to epimerization, giving a lower partial molar volume relative to the unit. give In roughly aprotic solvents, the 7-nomer effect is more pronounced than in alginate. Make profit.
出発材料として海草又は細菌起源のアルギネートを塩（アルカリ又はアルカリ出 金属形）、エステル又は他の酸誘導体のいずれかで選択することができる。Alginate of seaweed or bacterial origin is used as a starting material with salt (alkali or alkaline extract). (metallic form), esters or other acid derivatives.
超臨界二酸化炭素の適用は従来は不活性溶媒として超臨界流体を使用して例えば アロマ化合物の抽出内で主として見出されるエイチ・コーネンとイー・クリ−ゲ ル、食品工業における超臨界ガス抽出の利用（Ｈ，Ｃｏｅｎｅｎａｎｄ Ｅ、 Ｋｒｉｅｇｅｌ、［Ｕｓｅｓ ｏｒ ５ｕｐｅｒｃｒｉｔｉｃａｌ Ｇａ５Ｅｘ ｔｒａｃＮｏｎ ｉｎ ｔｈｅ Ｆｏｏｄ Ｉｎｄｕｓｔｒｙ Ｊ 、ムＣｈｅ ｉ＋、 肋１Ｔｅｃｈ、 ５５ （１９８３） ８９０ ） 。本発明に対する 基礎を形成する発明はポリサッカライドの非酵素的、化学的エピマー化の最初の 既知例および化学反応における触媒および溶媒の双方として超臨界流体の最初の 適用である。本発明は固体状態の材料に適用できることでこの種の酵素的および 大部分の他の既知化学的修飾方法とも異る。記載の既知方法は稀薄溶液（〈１％ ）を必要とし、そして生成物は沈澱させ、精製し、費用のかかる方法で乾燥しな ければならない。Applications of supercritical carbon dioxide have traditionally been performed using supercritical fluids as inert solvents, e.g. H. Konen and E. Kriege found primarily within the extraction of aromatic compounds. Utilization of supercritical gas extraction in the food industry (H, Coenenand E, Kriegel, [Uses or 5supercritical Ga5Ex tracNon in the Food Industry J, Mu Che i+, Rib 1 Tech, 55 (1983) 890). for the present invention The underlying invention is the first non-enzymatic, chemical epimerization of polysaccharides. Known examples and first examples of supercritical fluids as both catalysts and solvents in chemical reactions It is application. The present invention can be applied to solid-state materials to enable this type of enzymatic and It is also different from most other known chemical modification methods. The known method described uses a dilute solution (<1% ), and the product must be precipitated, purified, and dried in an expensive manner. Must be.
本発明では超臨界條件下で圧力を変えて（１５０〜５００バール）使用するＣｏ ２によりアルギネートを処理し、試験條件は変化に反映させたが、有意なエピマ ー化、ゲル強度の相当する増加はエピマー化に随伴した。従って、結果は超臨界 二酸化炭素処理によりグリクロナンス又は相当するオリゴサツカライドのＣ−５ エピマー化は炭水化物の化学的修飾に対する完全に新しい方法を供することを示 唆する。In the present invention, Co The alginate was treated according to 2, and the test conditions were reflected in the changes, but no significant epima was observed. -ization, a corresponding increase in gel strength accompanied epimerization. Therefore, the result is supercritical C-5 of glycronanthin or corresponding oligosaccharide by carbon dioxide treatment We show that epimerization offers a completely new approach to the chemical modification of carbohydrates. suggest
本発明の目的である化学的方法は次のように大きな経済的可能性を有する： Ａ） 固体状態材料に対し行なうことができる。The chemical method that is the object of the present invention has great economic potential as follows: A) It can be performed on solid state materials.
Ｂ）無毒性又は無害性化学薬品が必要で、従って生成物の精製を要しない。B) Requires non-toxic or non-hazardous chemicals and therefore does not require purification of the product.
Ｃ）超臨界流体による抽出に対する工業技術は既に他の目的に対し開発されてい るので方法は有利に大規模で行なうことができる。C) Industrial technology for extraction with supercritical fluids has not already been developed for other purposes. The method can advantageously be carried out on a large scale.
Ｄ） 方法はアルギネートのβ−Ｄ−マンヌロネート残基の工とマー化に限定さ れない。しかし、例えばＣ−６酸化セルロースのように他のポリサッカライドの エピマー化に対しても利用できる。その場合Ｄ−グルクロン酸はそのＣ−５エピ マー Ｌ−イドウ【Ｉン酸に転換する。相当する反応はムコポリサッカライド、 例えばフントリチン硫酸塩およびヒアルウロン酸の処理に利用できる。D) The method is limited to the engineering and merization of β-D-mannuronate residues in alginate. Not possible. However, other polysaccharides, such as C-6 oxidized cellulose, It can also be used for epimerization. In that case, D-glucuronic acid is Convert to mer L-idou [I phosphoric acid. The corresponding reaction is mucopolysaccharide, For example, it can be used to treat funtritin sulfate and hyaluronic acid.
例１： Ｌａｍ１ｎａｒｉａ 江肚叩匹對から単離したアルギン酸ソーダ（５０９）を鉄 製カラムに充填し、超臨界條件下でＣｏ２により処理した。圧は１５０〜５００ バールに変動させた。ガス流は０．５〜１０ｄ／分で、温度は４５℃、処理は１ ２時間継続した。材料の損失はすべての試験でく１％であった。ポリマー組成物 は広分野（４００ＭＨｚ）’ＨＮＭＲ分光器（第１図参照）により測定し、エイ チ・グラスダレン［アルギネートの高磁場１日ＮＭＲ分光分析法： 配列構造と 結合配座」（ＨｌＧｒａｓｄａｌｅｎ ｒＨｉｇｈ−ｆｉｅｌｄ １Ｈ−ＮＭＲ ５ｐｅｃｔｒｏｓｃｏｐｙ ｏｆ＾１ｇ１ｎａｔｅ： ５ｅｑｕｅｎｔｉａｌ ５ｔｒｕｃｔｕｒｅ ａｎｄ ＬｉｎｋａｇｅＣｏｎｆｏｒｍａｔｉｏｎＪ 、 （１１■■ＤΔＪ二 Ｒｅｓ、１１８ （１９８３） ２５５〜２６０）それぞ れ２つのモノマー ユニット、ＭおよびＧのモルフラクションとして、Ｆ およ びＦ６（この場合Ｆ ＋ ＦＧ −１）として、および配列パラメータ又は４つ の「もつとも近い隣接」配列、ＭＭ、ＧＧ、ＭＧおよびＧＭ（この場合Ｆ ＋Ｆ ＋２ＦＨＧ＝ １ ）として第Ｉ８８ ＧＧ 表に示す。Example 1: Sodium alginate (509) isolated from Lam1naria The sample was packed into a manufactured column and treated with Co2 under supercritical conditions. Pressure is 150-500 It was changed to crowbar. The gas flow was 0.5-10 d/min, the temperature was 45 °C, and the treatment was 1 It lasted for 2 hours. Material loss was 1% in all tests. polymer composition is measured using a wide-field (400 MHz) HNMR spectrometer (see Figure 1). High-field 1-day NMR spectroscopy of glasdalene [alginate: array structure and "Bound conformation" (HlGrasdalen rHigh-field 1H-NMR 5pectroscopy of＾1g1nate: 5equential 5structure and LinkageConformationJ, (11■■DΔJ2 Res, 118 (1983) 255-260) As a morphological fraction of two monomer units, M and G, F and and F6 (in this case F + FG -1), and array parameters or four 'nearest neighbor' sequences, MM, GG, MG and GM (in this case F + F +2FHG=1) as No. I88 GG Shown in the table.
第工表の結果はＣＯ□処理が３つの異る圧力條件下でグルロネート含量に有意の 増加を生じたことを示す。The results in Table 1 show that CO□ treatment has a significant effect on guluronate content under three different pressure conditions. Indicates that an increase has occurred.
ＦＧで表わした含量は未処理材料の０．５２（すなわち、５２％）から処理後０ ．６０．０．６４および０．６６に変化した。最高圧（５００バール）は組成に 最大の変化を生じた。The content in FG ranges from 0.52 (i.e. 52%) in the untreated material to 0 after treatment. ．． 60. Changed to 0.64 and 0.66. Maximum pressure (500 bar) depends on the composition produced the greatest change.
Ｇ含量のこの増加は多価イオンによるゲル形成能力の増加したアルギネートを形 成した。第■表はＣＯ２処理ポリマーのいくつかの物理的性質を示す。粘度はプ ルツクツイールド粘度計で測定し、固有粘度〔η〕はカンノン−ウベローデ毛細 管粘度計で測定した。１％アルギン酸カルシウムゲルのゲル強度はＦＴＲＡゲル 強度装置で測定し、２％均質カルシウムゲルの硬さ係数はスチープンス テクス チャー アナライザーで測定した（ジー・スキアク・ブラック、ピー・ジーセン およびオー・スミズロド［試験管内酵素修飾によるアルギネートのテーラリング Ｊ ） （Ｇ、 ５ｋｊａｋ−Ｂｒａｅｋ、 Ｂ、 Ｌａｒｓｅｎ ａｎｄ Ｏ 。This increase in G content forms alginate with increased gel-forming ability due to multivalent ions. accomplished. Table 1 shows some physical properties of CO2 treated polymers. The viscosity is The intrinsic viscosity [η] was measured using a Lutsk Twield viscometer, and the intrinsic viscosity [η] was a Cannon-Ubbelohde capillary. Measured with a tube viscometer. Gel strength of 1% calcium alginate gel is FTRA gel The hardness coefficient of the 2% homogeneous calcium gel was determined using a strength device by Steepens Tex. Measured with a char analyzer (G. Schiak Black, P. Giesen) and O. Sumizrod [Tailoring of alginate by in vitro enzymatic modification] J) (G, 5kjak-Braek, B, Larsen and O .
Ｓｍ１ｄｓｒｏｄ ｒ Ｔａ１ｌｏｒｉｒ＋ｇｏｆ Ａｌａｉｎａｔｅ Ｂｙ ＥｎｚｙｍａｔｉｃＭｏｄｉｆｉｃａｔｉｏｎ ｉｎ ｖｉｔｒｏ Ｊ 、 Ｉ ｎｔ、去Ｂｉｏ１． ＨａＣｒｏｌｌｏｌ。Sm1dsrod r Ta1lorir+gof Alainate By Enzymatic Modification in vitro J, I nt, left Bio1. HaCrollol.
８ （１９８６） ３３０〜３３６）。8 (1986) 330-336).
ＣＯ２処理は固有粘度の減少を生じた。グリコシド結合の加水分解開裂により生 ずると推定する。しかし、限定的分解はアルギネートのゲル形成性に全く影響を 有しない。ＦＴＲＡ値および硬さ係数の双方によるゲル強度は明白な増加を示し 、ラミナリア・ハイパーボリア（Ｌａｍ１ｎａｒｉａ ｈｙｐｅｒｂｏｒｅａ） の茎から得たもつとも強いゲル形成性アルギネートに対し見出されるものに匹敵 できる値を得た。CO2 treatment resulted in a decrease in intrinsic viscosity. Produced by hydrolytic cleavage of glycosidic bonds Presumably cheat. However, limited degradation has no effect on the gel-forming properties of alginate. I don't have it. Gel strength by both FTRA value and hardness coefficient showed a clear increase. , Laminaria hyperborea (Lam1naria hyperborea) Comparable to that found for the very strong gel-forming alginate obtained from the stems of I got the value I could.
第工表 ＦＧＦＨＦＧＧＦＧＨＦ団 未処理試料 ０．５２ ０．４８ ０．３４ ０．１８ ０．３０１５０バール ０．６０ ０．４０ ０．５０ ０．１０ ０．３０２５０バール０．６４ ０．３６ ０．５５ ０．０９ ０．２７５００１＜−ル０．６６ ０．３４ ０，５３ ０．１３ ０．２１ＣＯ２処理アルギネートの物理的性質 未処理試料 ２０５ ８．８ ４０ ６．２１５０バール ８０．６ ６．９ ６３ −２５０バール ８６．２ ６．８ ６３．５ −５００バール ８０． ７ ６．９ ６３．５ ９．０例２ アスコフイラム・ノドスム（■９刃１匹ｕｎｏｄｏｓｕｍ ）から単離したポリ −マンヌロン酸のソーダ塩を２００バールおよび４５℃で超臨界ＣＯ２により１ ２時間処理した。損失はく０．５％であった。ポリマー中のグルロネート含量は く５％から１６％に増加した（第２図、参照）。結果はもとの完全なポリマーの Ω−マンヌ１コネートは所定條件下でＣ−５エピマー化することを明らかに示唆 する。No. 1 schedule FGFHFGGFGHF group Untreated sample 0.52 0.48 0.34 0.18 0.30150 bar 0.60 0.40 0.50 0.10 0.30250 bar 0.64 0.36 0.55 0.09 0.275001<-ru 0.66 0.34 0.53 0.13 0.21 Physical properties of CO2 treated alginate Untreated sample 205 8.8 40 6.2150 bar 80.6 6.9 63 -250 bar 86.2 6.8 63.5 -500 bar 80. 7 6.9 63.5 9.0 Example 2 Poly isolated from Ascophyllum nodosum (■9 blades 1 unodosum) - sodium salt of mannuronic acid at 200 bar and 45°C with supercritical CO2 It was treated for 2 hours. The loss was 0.5%. The guluronate content in the polymer is It increased from 5% to 16% (see Figure 2). The result is that of the original complete polymer. Clearly suggests that Ω-mannu1conate undergoes C-5 epimerization under certain conditions. do.
第１図 １、７の葉からのアルギネートの４００ＭＨｚ’Ｈｎ、ｍ、ｒ、スペクトル。Ａ ： し肚肚座と朋の葉からのアルギン酸ソーダ、５００バール、４５℃で１２時 間超超臨界性で００２により処理。Ｂ： 未処理アルギネート。修飾ポリマーの Ｇ含最の変化はｒＭＪシグナル（Ｉｆ）に比較してｒＧＪシグナル（工および■ ）の相対的強さの増加により実証される。Figure 1 400 MHz'Hn, m, r spectrum of alginate from leaves 1 and 7. A : Sodium alginate from Shibuzuza and Tomoha, 500 bar, 12 o'clock at 45°C Processed with 002 at super-supercriticality. B: Untreated alginate. modified polymer The most significant change in G content is in the rGJ signal (E and ■) compared to the rMJ signal (If). ) is demonstrated by an increase in the relative strength of
第２図 Ａ、 ｎｏｄｏｓｕ■から単離したポリマンヌロン酸ソーダの４００ＭＨｚ ’ Ｈｎ、ｍ、ｒ、スペクトル。Ａ） ２００バールで１２時間超臨界ＣＯ２により 処理。（Ｆ６−０、’１６） Ｂ） 未処理ポリ−Ｍ （Ｆｅ 、＜０．０５） 。Figure 2 A. 400MHz of sodium polymannuronic acid isolated from nodosu■ Hn, m, r, spectrum. A) By supercritical CO2 at 200 bar for 12 hours process. (F6-0, '16) B) Untreated poly-M (Fe, <0.05) .
スペクトルのシグナルエはＬ−グルロネート含鑓に相当する。The signal of the spectrum corresponds to L-guluronate inclusion.
ＰＰＭ。PPM.
ＰＯＬＹ Ｎ。POLY N.
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| NO864147 | 1986-10-17 | ||
| NO864147A NO160374C (en) | 1986-10-17 | 1986-10-17 | PROCEDURE FOR MODIFICATION OF ALGINATES (POLYURONIDES) TO GET CHANGED PHYSICAL PROPERTIES. |
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| JP2012121963A (en) * | 2010-12-07 | 2012-06-28 | Meiji Univ | Method for producing polyguluronic acid, method for producing polymannuronic acid, polyguluronic acid, and polymannuronic acid |
| US9357231B2 (en) | 2008-07-31 | 2016-05-31 | Mitsubishi Electric Corporation | Video encoding device, video encoding method, video reproducing device, video reproducing method, video recording medium, and video data stream |
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| US5166137A (en) * | 1991-03-27 | 1992-11-24 | Nobipols Forskningsstiftelse | Guluronic acid polymers and use of same for inhibition of cytokine production |
| US5783627A (en) * | 1996-09-09 | 1998-07-21 | University Of Massachusetts | Dense gas-compatible enzymes |
| US5977348A (en) * | 1997-07-25 | 1999-11-02 | National Starch And Chemical Investment Holding Corporation | Polysaccharide modification in densified fluid |
| US20080108110A1 (en) * | 1998-04-02 | 2008-05-08 | Deangelis Paul L | Targeted glycosaminoglycan polymers by polymer grafting and methods of making and using same |
| US7223571B2 (en) * | 1998-04-02 | 2007-05-29 | The Board Of Regents Of The Universtiy Of Oklahoma | Targeted glycosaminoglycan polymers by polymer grafting and methods of making and using same |
| US20030104601A1 (en) * | 1999-04-01 | 2003-06-05 | Deangelis Paul L. | Chondroitin synthase gene and methods of making and using same |
| US20060188966A1 (en) * | 1998-04-02 | 2006-08-24 | Deangelis Paul L | Natural, chimeric and hybrid glycosaminoglycan polymers and methods of making and using same |
| US7642071B2 (en) | 1999-04-01 | 2010-01-05 | The Board Of Regents Of The University Of Oklahoma | Methods of expressing gram-negative glycosaminoglycan synthase genes in gram-positive hosts |
| FR2873700B1 (en) * | 2004-07-29 | 2006-11-24 | Centre Nat Rech Scient Cnrse | PROCESS FOR THE CONTROLLED OXIDATION OF POLYSACCHARIDES |
| MX2009000255A (en) | 2006-07-04 | 2009-04-07 | Spermvital As | Preservation and controlled delivery/release of spermatozoa. |
| WO2009134368A2 (en) * | 2008-04-29 | 2009-11-05 | Marshall University Research Corporation | Methods of producing bacterial alginates |
| GB201120368D0 (en) | 2011-11-24 | 2012-01-04 | Sperm Vital As | Methods for the preparation of hydrogels |
| FR2994387B1 (en) * | 2012-08-13 | 2016-07-29 | Basf Beauty Care Solutions France Sas | COSMETIC OR PHARMACEUTICAL MOISTURIZING INGREDIENT |
| CN104341535B (en) * | 2013-08-07 | 2018-09-14 | 青岛博研达工业技术研究所(普通合伙) | A kind of high-valued extracting method of Enteromorpha |
| CN104341233A (en) * | 2013-08-08 | 2015-02-11 | 青岛博研达工业技术研究所(普通合伙) | Method for high-efficiency extraction of nutrient substances in undaria pinnatifida sporophyll |
| CN104341536A (en) * | 2013-08-08 | 2015-02-11 | 青岛博研达工业技术研究所(普通合伙) | Method for high-efficiency extraction of nutrient substances in seaweed |
| CN104341537A (en) * | 2013-08-08 | 2015-02-11 | 青岛博研达工业技术研究所(普通合伙) | Method for arsenic removal and extraction of nutrient substances in sargassum fusiforme |
| RU2691990C2 (en) * | 2015-03-19 | 2019-06-19 | Дмитрий Викторович Незговоров | Alginic acid derivative |
| DK3547834T3 (en) | 2016-12-05 | 2021-11-08 | Spermvital As | COMPOSITION WITH LONG-TERM RELEASE |
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| NO845059L (en) * | 1984-12-17 | 1986-06-18 | Sintef Inst For Marin Biokjemi | PROCEDURE FOR PREPARING ALGINATES WITH CHANGED PHYSICAL PROPERTIES AND USING THESE ALGINATES. |
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1988
- 1988-06-15 KR KR1019880700678A patent/KR880701738A/en not_active Application Discontinuation
- 1988-06-16 FI FI882884A patent/FI882884A/en not_active IP Right Cessation
- 1988-06-16 SU SU884356051A patent/SU1804464A3/en active
- 1988-06-16 RO RO134025A patent/RO104348B1/en unknown
- 1988-06-16 DK DK330688A patent/DK330688A/en not_active Application Discontinuation
- 1988-06-16 MW MW24/88A patent/MW2488A1/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9357231B2 (en) | 2008-07-31 | 2016-05-31 | Mitsubishi Electric Corporation | Video encoding device, video encoding method, video reproducing device, video reproducing method, video recording medium, and video data stream |
| JP2012121963A (en) * | 2010-12-07 | 2012-06-28 | Meiji Univ | Method for producing polyguluronic acid, method for producing polymannuronic acid, polyguluronic acid, and polymannuronic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| BR8707509A (en) | 1989-02-21 |
| DK330688D0 (en) | 1988-06-16 |
| WO1988002758A1 (en) | 1988-04-21 |
| HU202251B (en) | 1991-02-28 |
| NO864147L (en) | 1988-04-18 |
| MC1937A1 (en) | 1989-05-19 |
| AU604070B2 (en) | 1990-12-06 |
| NZ222182A (en) | 1990-06-26 |
| RO104348B1 (en) | 1993-04-25 |
| FI882884A0 (en) | 1988-06-16 |
| EP0288494A1 (en) | 1988-11-02 |
| KR880701738A (en) | 1988-11-04 |
| ES2007422A6 (en) | 1989-06-16 |
| US4990601A (en) | 1991-02-05 |
| NO864147D0 (en) | 1986-10-17 |
| EP0288494B1 (en) | 1993-05-05 |
| DE3785754T2 (en) | 1994-01-05 |
| IL84177A (en) | 1992-11-15 |
| FI882884A (en) | 1988-06-16 |
| NO160374B (en) | 1989-01-02 |
| HUT52118A (en) | 1990-06-28 |
| DK330688A (en) | 1988-06-16 |
| PH23281A (en) | 1989-06-23 |
| DE3785754D1 (en) | 1993-06-09 |
| ATE89008T1 (en) | 1993-05-15 |
| AU8074987A (en) | 1988-05-06 |
| MW2488A1 (en) | 1989-02-08 |
| SU1804464A3 (en) | 1993-03-23 |
| NO160374C (en) | 1989-04-12 |
| IL84177A0 (en) | 1988-03-31 |
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